MXPA99003412A - Lubricity additives for fuel oil compositions - Google Patents

Abstract

Specific substituted aromatic amide compounds are useful as lubricity additives for middle distillate fuel oils.

Description

LUBRICATING ADDITIVES FOR COMBUSTIBLE OIL COMPOSITIONS This invention is relased additives to improve the lubrication of fuel oils such as diesel fuel oil. The diesel fuel composition that includes the additives of this invention have improved lubrication and reduced engine wear. Concern for the environment has resulted in sambios to significantly reduce the harmful components in emissions when fuel oils are burned, particularly in machines such as diesel engines. Attempts have been made, for example, to minimize sulfur dioxide emissions. As a consequence, attempts have been made to minimize the sulfur content of the combustible substances. For example, although typical diesel fuel oils in the past contained 1 weight percent or more of sulfur (expressed as elemental sulfur) it is now considered desirable to reduce the level to 0.2 weight percent, preferably to 0.05 weight percent and , advantageously, less than 0.01 weight percent, particularly less than 0.001 weight percent. The additional refining of the fuel oils, necessary to achieve these low sulfur levels, often results in redusions at the level of the polar components. In addition, refinery processes can reduce the level of polynuclear aromatic compounds present in these fuel oils. The reduction of the level of one or more of the sulfur, poly-molluscan or polar somatic components of the diesel fuel may reduce the sapity of the oil to lubricate the engine's injector system so that, for example, the fuel injection pump The engine fails relatively early in the life of an engine. The failure can occur in the fuel injection systems such as high pressure rotary distributors, pumps and injector in line. The problem of poor lubrication in diesel fuel oils is likely to be exacerbated by future engine developments that are aimed at further reducing emissions, which will have lubrication requirements more stringent than current engines. For example, the advent of high-pressure unit injectors anticipates the increase in the lubrication requirement of the fuel aseptide. Similarly, poor lubrication can lead to wear problems in other mechanical devices dependent for lubrication in the natural lubrication of the fuel oil. Lubricating additives for fuel oils have been described in the art. W0 94/17160 discloses an additive which comprises an ester of a sarboxylyous acid and a alsohol in which the acid has from 2 to 50 carbon atoms and the alcohol has 1 or more carbon atoms. The glycerol mono-oleate is specifically described as an example. Acids of the formula "R1 (COOH)", wherein R1 is an aromatic hydrocarbyl group are dessriben generically but are not exemplified. U.S. Patent No. A-3,273,981 discloses a lubricant additive which is a mixture of A + B wherein A is a polybasic acid, or an ester of polybasic acid, made by reacting the acid with monohydric alcohols with from 1 to 5 carbon atoms, wherein B is a partial ester of a polyhydric alcohol and a fatty acid, for example glycerol mono-oleate, sorbitan mono-oleate or pentaerythritol mono-oleate. The mixture finds aplissation in turbosinas. GB-A-1,505,302 discloses sombinasiones of esters that include, for example, monoesters of glycerol and glycerol diesters as diesel fuel additives, the combinations are described as leading to the advantages include less wear of the fuel injection equipment, of the rings of the pistons and the linings of the cylinders. The GB-A-1, 505, 302, however, is concerned with overcoming the operational disadvantages of corrosion and wear by products of acid combustion, waste in the combustion chamber and in the essape system. The dossier shows that these disadvantages are due to the incomplete combustion under siepera operasión sondisiones. The typical diesel fuels available up to the fesha of the second fuel were, for example, 0.5 to 1 per weight by weight of sulfur, as elemental sulfur, based on the weight of the fuel. U.S. Patent No. 4,087,273 describes lubricant additives which are products of the reaction of a solid disarboxylyl and a glisol, insoluble in oil. The acid is typically predominantly in dimer of unsaturated fatty acids such as linoleic acid or oleic acid, although minor proportions of the monomeric acid may be present. Only allyne diols or oxa-alsan diols are specifically suggested as the glycol reactant. U.S. Patent No. 4,090,971 and EP-A-0 719 761 disclose sodium amides of acid sarboxyls substituted hydroxychromatoxides, these materials being described as useful as dispersant additives for lubricants and fuels, respectively. No mention is made of medium distillation fuels with low sulfur content or how to solve their corresponding problem of poor lubrication. U.S. Patent No. 5,089,158 describes amide derivatives of an aromatic carboxylic acid having an ortho-hydroxy group in the form of a salt are a multivalent metal ion formed from amide pressurizers via an intermediate ester. The salts thus formed are preferably overbased. There is a continuous need for lubricant additives that show improved performance, due not only to the development of machines with more stringent requirements, but also to the general demand of consumers and producers of fuel for better quality fuels. In addition, there is a crescent need in the tisane for "multifunctional" additive compositions. These compositions provide a range of performance-improvement functions, typically through the insorption in them of several individual additives each having its own function. The resulting complex meshes often require addition to the fuel in relatively large quantities, and may also suffer from physical and chemical interaction problems between the individual additives that may deteriorate their subsequent performance in the fuel. The provision of an individual additive with multiple performance-enhancing effects can reduce or avoid the need for these complex compositions and their associated problems. It has now been found that certain amides of specific substituted aromatic carboxylic acids show improved lubrication performance. Some of these amides can also impart other performance eff ects to the fuming aseites are low sulfur content. In a first aspesto, this invention provides a somposision of asemite aseite that can be obtained by the adisión of a smaller proporsión of a sompuesto that somprende one or more aromatic ring systems where at least one of the ring systems leads, as substituents; (i) one or more hydrocarbyl groups that impart oil solubility to the compound, and (ii) one or more hydroxyl groups or derivatives thereof or both, and (iii) one or more amide groups, to a greater proportion of an oil a mean liquid hydrocarbon distillation fuel having a sulfur consension of 0.2 by weight or less, based on the weight of the fuel. In a second aspect, this invention provides a composition of non-combustible asexible that can be obtained by adduction, to the combustible asex defined under the first aspect, of an additive or concentrated composition in which the compound defined under the first aspect has been insorporated. In a third aspect, this invention provides a structure that comprises one or more systems of aromatic rings, wherein at least one of the ring systems carries, as substituents; (i) one or more hydrocarbyl groups that impart oil solubility to the compound, and (ii) one or more hydroxyl derivatives with the formula -OR 'wherein R' is hydrocarbyl or a group of the formula Hydrocarbyl -. { - M - alkylene - ^ - wherein M represents an oxygen atom or an NH group and n represents a number from 1 to 50, and (iii) one or more amide groups. Other aspects of this invention include an additive composition in which the compound of the third aspect has been incorporated, and an additive obtained by incorporating the compound or the additive composition and optionally one or more additional additives, into a mutually compatible solvent therefor. . The compounds defined under the first aspect of the invention provide, under the addition of the medium distillate fuel oil with low sulfur content, an improvement in the lubrication of the fuel oil. In particular, the specific compounds defined under the first aspect, which include the compounds claimed under the third aspect, give higher lubrication performance even at treatment regimes as low as 15 to 50 parts per million by weight, by weight of the fuel oil . In addition, some of these compounds can impart other performance-enhancing characteristics to the fuel oils, particularly detergency of the engine's inlet fuel systems and especially fuel injectors, reduced oxidation tendency especially during storage, and the sapacity to disperse insoluble which could otherwise lead to harmful deposits and / or blockages in the fuel line. The detergency and scattering advantages may be apparent for the components wherein one or more of its components (ii) is a derivative of a hydroxyl group of the formula OR7 as described hereinafter. The Fuel Oil Composition of the first aspect of the invention. A. The Compound The compound may comprise one or more aromatic ring systems. By "aromatic ring system" in this specification we mean a flat cylislase fraction which can be a homocyclic, heterocyclic or polycyclic aromatic fused assembly or a system where two or more of these mismatched assemblies are joined together and in the suals the cyclic assemblies can be the same or different. It is preferred that the or each aromatized ring system is a system based on 5 or 6 membered heterocyclic or homocolic rings, more preferably 6 membered rings and more preferably bensen rings. The ring atoms in the aromatic system are preferably carbon atoms but may for example include one or more heteroatoms such as N, S, or O in the system in which case the compound is a heterocyclic compound. Examples of suitable polycyclic assemblies include (a) dense benzene structures such as naphthalene, anthracene, phenanthrene and pyrene; (b) ring-shaped structures wherein none or all of the rings are bensen such as azulene, indene, hydroindene, fluorene, and diphenylene; (c) "end-capped" rings such as biphenyl; and (d) heterocyclic compounds such as quinoline, indole, 2: 3 dihydroindole, benzofuran, benzothiophene, carbazole and thiodiphenylamine. When the compound comprises only one aromatic ring system, this system necessarily bears the three types of substituent (i), (ii) and (iii). It is preferred that one of each of the substituents (ii) and (iii) be present in this compound. It is also preferred that one, two or three substituents (i) be present, with less one of which being capable of imparting oil solubility to the compound. When the composition comprises two or more aromatic ring systems, it is preferred that at least two, preferably each of the systems carry the three types of substituents (i), (ii) and (iii). It is preferred that each system carrying these three types of substituents bears one of each of the substituents (ü) and (iii), and preferably one, two or three substituents (i), subject to the requirement that at least one of the Substituents (i) provide solubility in oil to the compound. Partially preferred are the compounds where the one or more of the aromatic ring systems is a single 6-membered ring, especialy a benzene structure. More preferably, the compound comprises a single benzene ring and one, two or three (preferably one or two) of the substituents (i) and having one of each of the substituents (ii) and (iii), wherein the substituent (ii) is a hydroxyl group. The substituent (i) is a hydrocarbyl group. By the term "hydrocarbyl" in this description we mean an organismal fraction which is hydrogen and sarbonate, the sual is bound to the rest of the molecule by an atom or carbon atoms which unless otherwise stated, it can be aliphatic, including alisísliso, aromatiso or a combination of the same. It may be a substituted or unsubstituted alkyl, aryl or alkaryl and may optionally contain unsaturation or heteroatoms such as O, N or S, provided that these heteroatoms are insufficient to alter the essentially hydrosarburo nature of the group. It is preferred that the substituent (i) is aliphatic, for example alkyl or alkenyl, which may be branched or preferably substituted. Alkaline sacrament is preferred. Alternatively the substituent (i) may comprise a branched or preferably linear alkyl or alkenyl chain interrupted and / or substituted by one or more oxygen, sulfur or especially nitrogen atoms. Suitable examples include a substituent comprising one or more amino groups and optionally terminated by an amino group. Preferred substituents of this class include straight-chain alkyl groups terminally and / or internally substituted by one or more amino groups; and the substituents obtained from the Mannich-type condensation reaction of an alkylene diamine, aldheido and the aromatic ring system in which the substituent (i) is required, the reaction resulting in the formation of a substituent (i) of the formula : H 2 N-f-alkylene-f- N I - CH R wherein the alkylene represents the alkylene segment of the reactive diamine and R represents the substituent that is derived from the aldheido. Thus, for example, when for aldheido is used in the formation of the above substituent (i), R will represent hydrogen, higher aldheyds which result in the formation of a supending substituent which is preferably alkyl and more preferably alkyl of sub stitue. It is essential for the good performance of the compound that at least one substituent of the formula (i) is a hydrosarbyl group of oleophilic saráster sufissent to impart oil solubility to the compound. Regarding this, it is preferred that at least one substituent (i) contains at least 8 carbon atoms, and preferably from 10 to 200 carbon atoms. A substituent having from 12 to 54, for example from 14 to 36 carbon atoms, is particularly preferred. More preferred are alkyl or alkenyl groups which are of 12 to 54 carbon atoms, especially straight chain alkyl groups. Groups having 14 to 20 carbon atoms are the most advantageous. Also preferably, this substituent (i) contains no more than 5 heteroatoms or groups containing heteroatoms and more preferably no more than 3 of these atoms or groups, such as 2 of these atoms or groups. Provided that the compound possesses at least one hydrocarbyl substituent (i) imparting the required solubility in oil, any additional substituent (i) may be of any proportioned character that does not adversely interfere with the oil solubility of the compound. In this way, these additional substituents (i) can contain any number of sarbono atoms and can also be interrupted by heteroatoms or groups containing heteroatoms, and / or substituted by groups containing heteroatoms. A mixture of coatings differing in these additional substituents (ii) can be used. In particular, these substituents can be derived from alkylene diamines or polyalkylene polyamines via the Mannich-type condensation reaction described above; these products can also provide particularly advantageous dispersion and detergent properties to the resulting compounds. The amines or polyamines substituted by hydroxyl can also be used to form coatings having especially good multifunctional astivity. The substituent (ii) is a hydroxyl group or derivative thereof, and may be represented by the formula -ORI When it is a hydroxyl group, the compound may show particularly good performance as an oxidation inhibitor. The hydroxyl group can be derivatized in a sapaz substituent to impart another multifunctional saráster, for example a group of the form -OR 'wherein R' is hydrocarbyl as described hereinabove in relation to the substituent (i), or a straight-chain or branched alkylene-oxyhydrocarbyl or poly (alkylene-oxy) hydroxycarbyl group and / or an alkyd-hydroxycarbyl or poly (alkyleneamino) hydroxycarbyl group of linear or branched chain having the formula: Hydrocarbyl M- Alkylene -) - - where M represents an oxygen atom or an NH group and n represents a number from 1 to 50, preferably from 2 to 20, more preferably from 2 to 10, for example from 3 to 5; and wherein the hydrocarbyl is as previously defined and especially can be substituted, preferably terminally substituted, by a heteroatom-containing group, for example a hydroxyl or amino group. Small hydrocarbyl groups, such as those containing 1 to 24, preferably 1 to 18, for example 2 to 12 carbon atoms are particularly advantageous. The alkylene group may contain from 1 to 6, for example from 2 to 4 methylene units and may also optionally be substituted by a group or groups containing heteroatoms. R7 can be linked directly to the oxygen that depends on the ring system or indirectly via a linking group, such as a carbonyl group. Hydroxyl group-containing heteroatoms, useful as a substituent (ii), can show particular benefit in providing dispersing and / or detergent properties when used in preferred fuel oils. Preferred with respect to this are the derivatives of the formula: O (CH2) NH2 n ' wherein n represents a number from 1 to 24, preferably from 1 to 18, more preferably from 1 to 6, particularly 3. The substituent (iii) is an amide group, wherein the carbonyl carbon of the amide is preferably directly bound to a ring atom of the aromatic ring system, and more preferably to a ring sarbon. The amide group preferably has the formula OR II R "C N R" Where the group -NR "R '• * is derivable from the corresponding amide HNR" R' • *, where R "and R1" each independently represents hydrogen or a hydrocarbyl group as previously defined, and especially one that has from 1 to 30, for example from 1 to 22 carbon atoms and optionally substituted by heteroatoms or heteroatom-containing groups, or R "and R '* • each independently represents a poly (alkylene-oxy) alkyl or poly ( alkyleneamino) alkyl, also optionally so substituted. Preferably at least one, and more preferably the or each substituent (iii), is derivable from a primary amine or compound containing at least one primary amine group. In this way, for example, when the substitute te (iii) has the formula OR II • R "c N R" one of the substituents R "and R '' 'in the amide group is hydrogen The remaining substituent is preferably a hydrocarbyl group, or a hydrocarbyl group interrupted by amino and / or substituted by amino, wherein the hydrosarbyl group is preferably alkyl, more preferably normal alkyl These amides are derivable, for example, from amines such as hydrosarbyl amines, and hydrosarbylene diamines and polyhydrocarbylene polyamines having at least one primary amine group Other amine groups, when present, may be amine groups primary, secondary or tertiary These amines may also conveniently be substituted by other groups containing heteroatoms, such as hydroxyl groups or derivatives thereof.

Particularly good results have been achieved when the amine of the sual is derivable the amide group is an alkylene diamine. Convenient diamines can have one or two preferably primary amino groups and between 1 and 50, for example from 2 to 10, preferably from 2 to 6 carbon atoms preferably in a straight alkylene chain. When the diamine contains a primary amino group, the other group can be a secondary or tertiary amino group. Particularly convenient examples include N, N-dimethyl-1,3-propanediamine; N, N-dimethyl-l, 2-propanediamine; N, N-dimethyl-1,2-ethanediamine; and its substituted N, N-diethyl and N, N-dipropyl homologs. N, N-dimethyl-1,3-propanediamine is most preferred. When the diamine contains 2 primary groups, especially convenient examples include 1,2-ethanediamine; 1,2- and 1,3-propanediamines; and 1,2-, 1,3- and 1,4-butanediamines. The most preferred is 1,2-ethanediamine. Particulary good results have also been cast by stirring the amine from which the amide group is derivable is a polyalkylene polyamine. Suitable amines include those containing 1 or 2 amino groups and between 2 and 50, for example between 4 and 20 carbon atoms, and preferably between 6 and 12 carbon atoms, preferably in a series of straight alkylene segments. These amines include those of the general formula H2N - (- alkylene NH - - H where the alkylene represents a straight chain alkylene segment preferably containing 2 to 4 carbon atoms, and x represents a number of 2 to 4 carbon atoms. 10, preferably from 3 to 6. Mixtures of these polyalkylene polyamines can be used with good results, as they are produced typically somersially.These mixtures can also obtain polyamines in which the "alkylene" can represent branched chain or silica units. Particularly convenient polyalkylene polyamines are polyethylene polyamines such as diethylenetriamine; triethylenenetetramine; tetraethylenepentamine and pentaethylenehexamine, and mixtures thereof. The mixtures are typically described with reference to the polyamine to which the approximate average somatinity is approximated; thus, "a mixture approaching tetraethylenepentamine" is one in which the average number of nitrogens per molecule of polyamine approaches 5. Triethylenenetetramine, tetraethylenepentamine and pentaethylenehexamine are more preferred as useful amine materials to form the amides of this invention, with pentamine mixtures being most preferred. The polyamine analogs of polypropylene and polybutylene, and mixtures thereof, are also suitable amines to form the amides used in this invention.

Other useful amines are polyhydroxylamines which give rise to amide groups which form alkyl substituents substituted by hydroxy. Suitable polyhydroxylamines are straight or branched chain hydroxyamines, aliphatisates, saturated or unsaturated, having from 2 to 10, preferably from 2 to 6, more preferably from 2 to 4, hydroxyl groups, and having from 2 to 90, preferably from 2 to 30, more preferably 2 to 12, more preferably 2 to 5 carbon atoms in the molecule. In the compound, the substituents (ii) and (iii) are preferably placed in the vicinity of the aromatic ring system on which they depend. When the system is polycystose, they are preferably soldered vesinally in the same ring of the polycyclic system, for example in a position ortho to one another, although they can be placed in different rings. The or each substituent (i) can be solosar local to any of the substituents (ii) or (iii), or in a more removed position in the ring system. The compound can also be of oligomeric structure, for example a series of aromatic ring systems are shown via alkylene bridges produced, for example, by the reassess of phenol-formaldehyde-type denudation of various aromatic ring systems with an aldheido; or an oligomer containing 2 or more aromatic ring systems in the ring-suds is amidated to a different nitrogen of the same di- or poly-amine. Particularly useful are bridged methylene compounds wherein each aromatic ring system is preferably a homozygous 6-membered ring and wherein, more preferably, each ring carries at least 1 of each of substituents (i), (ii) and (iii). A preferred form of the filler can be represented by the following general formula (I): wherein Ar represents an aromatic ring system, -B, -OR * and -C0NR "R * * 'represent the substituents (i), (ii) and (iii) respectively as defined hereinabove, and A represents a group of the formula (II): wherein Ar, B, R, R "and R * '• are as previously defined herein in formula (I) and A' and A" each independently represents hydrocarbylene groups, and wherein: v represents an integer in the range from 0 to 10; represents an integer in the range from 0 to 3; and x, y and z each independently represents an integer in the range of 1 to 3. Preferably, R 'represents hydrogen, or a hydrocarbyl group, or a poly (alkylene-oxy) alkyl or poly (alkylene-amino) alkyl group optionally substituted by one or more heteroatom-containing groups, and wherein R 'can be linked either directly to the oxygen that depends on the ring system, or indirectly via a linking group; R "and R '' 'preferably independently represent hydrogen or a hydrocarbyl group optionally substituted by one or more heteroatom-containing groups, or a poly (alkylene-oxy) alkyl or poly (alkylene-amino) alkyl group, also optionally so substituted, or other preferences of R "and R * * 'described above herein. Preferably, x represents 1 or 2, especially when y and z each represents 1. When w is from 1 to 3, v is preferably from 1 to 9, for example from 2 to 5, such as 3. Alternatively, v can be 0 ( zero) . Preferably A 'and A "are methylene or substituted methylene groups When w = o, the compound comprises a single aromatic ring system having substituents (i), (ii) and (iii) It is preferred that when = 0, yyz sada one is = 1 and x = 1 or 2, more preferably, R "represents an alkyl, alkylene amino or polyalkylenepolyamino group and R 'and R * •' represent hydrogen. More preferably, Ar represents a benzene ring; = 0; x = l or 2; y and z each = 1; R "represents an alkyl group and R 'and R *" represent hydrogen.More preferably, the compound is ethane-1,2-diamine or tetraethylene-pentamine-amide of the acidic salisyl-substituted alkyl., the substituent or the alkyl substituents of the acid containing between 14 and 18 carbon atoms. The mechanism of action of the compound is not clearly understood. However, it is postulated that the system or the specific substituted aromatic ring systems form a flat region within the molecule, the hydroxyl group or hydroxyl derivative and the amide group and substituents of the group that contribute to an electronic and polar character Through this flat region, which is surprisingly effective in the adsorption of the surface and to improve the ability of fuels to lubricate metallic surfaces srítisas in the injection system, and particularly in the bomb of insesssión. The compound can be prepared by conventional means. Thus, for example, the filler can be prepared by amidating a precursor compound having the required aromatic ring system or systems carrying the substituent (s) (i), substituent (s) (ii) and one or more carboxylic acid substituents, or asilassion derivatives thereof, capable of amidation are stacked having less than one amino group to form the substituent (iii). The resulting derivatives of asilasión insulate esters, anhydrides and halides halides. A convenient method for the preparation of the amides is described in U.S. Patent No. 4,090,971, column 5, line 34 to column 6, line 25, the description of this method being part of the breakdown of this invention. The somatic pressurizer can be prepared by the hydrosarbarylation of a suitable hydroxyl-substituted aromatic ring system compound, for example by an electrophilic substitution reaction using a halide derivative of the desired hydrocarbyl substituents, for example via a Friedel-Crafts-type reaction using slurry. Iron catalyst (iii) • Alternatively, hydrocarbylation can be achieved through the reaction of the corresponding alkylene using a catalyst system of hydrogen fluoride and boron trifluoride, or a catalyst system of hydrogen chloride and aluminum trichloride. The resulting hydroxyl-substituted hydroxyl-substituted aromatic compound may be carboxylated, for example via the "Kolbe-Schmitt" reaction which results in the reaction of a salt, preferably an alkali metal salt, of the hydroxyl-substituted aromatic compound, substituted by hydroxyl they are sarbono dioxide and later assimilating the salt thus obtained. Alternatively, a product of the Friedel-Crafts asselation type may be used to add the required sarboxylic acid substituents. This acid can be derived in an acylation group such as an ester group, an anhydride group or an acid halide group, for example an acid chloride group, to facilitate the subsequent amidation reaction. The previous types of the reaction are very conosidos in the chemise teésnisa. Preferred precursor compounds are carboxylic acid derivatives of phenols and / or naphthols substituted by hydrocarbyl, with phenols being most preferred. Particularly preferred are the substituted hydrocarbyl salicylic acids which typically comprise a mixture of mono- and disubstituted asides. These materials are readily available in a convenient form for the amidation reaction without the need for further modification. B. The combustible aseil of medium distillation. The fuel oil has a sulfur consension of 0.2 per cent by weight or less based on the weight of the fuel, and preferably 0.05 per cent or less, more preferably 0.03 per cent or less, such as 0.01 percent or less, more preferably 0.005. percent or less and especially 0.001 percent or less. These fuels can be made by means and methods known in the technique of producing fuels, such somo extrassion of solvent, hydrodesulfurizaión and treatment by sulfuric acid. As used in this descriptive report, the term "distillation medium distillation asease" includes a petroleum product obtained by refining crude oil as a frassion between the lighter kerosene and the frassion of turbosines and the frassión of heavier fuel oil. These distillate fuels generally have the boiling point in the range of about 100aC, for example 1509 to about 4002C, and those having a relatively high 95 percent distillation point above 360 ° C (measured by ASTM-D86) are included. In addition, "automotive diesel" type fuels, which have a 95 percent lower distillation point of 260-330eC and particularly also sulfur containing less than 200 ppm, preferably 50 ppm and particularly 10 ppm (w / w) are they include within the term "medium distillation fuel oil". The intermediate distillates contain a boiling dispersion of hydrocarbons over a temperature range, which include normal alkanes which precipitate as wax as the fuel cools. It can be characterized by the temperatures in which several percentages of fuel have been vaporized ("distillation point"), for example 50 percent, 90 percent, 95 percent, with intermediate temperatures at which a certain percentage of volume of inisial fuel has been distilled. They are also characterized by points of fluidity, turbidity and CFPP, as well as their initial boiling point (PEI) and point of distillation at 95 by feel or final boiling point (PEF). The fuel oil may comprise atmospheric distillate or vacuum distillate, or disintegrated gas oil or a mixture in any proportion of direct distillates and thermally and / or catalytically disintegrated. The most common intermediate distillate petroleum fuel oils are diesel fuels and heating oils. The diesel fuel or the heating oil can be a direct atmospheric distillate or it can contain small amounts, for example, up to 35 weight percent, of gas oil to the vessel or disintegrated gas oils or both. The salting outlets can be made from a mixture of virgin distillate, for example gas oil, naphtha, etc. and disintegrated distillates, for example satatalis cis-material. A representative diesel fuel density includes a minimum flash point of 389C and a 90 percent distillation point of 282. 380SC (see the designations of ASTM D-396 and D-975).

As used in this specification, the term "medium distillate fuel oil" also extends to biofuels, or biofuel mix with medium distillate petroleum fuels. Biofuels, ie fuels from animal or vegetable sources are believed to be less harmful to the environment in combustion, and are obtained from a renewable source. Certain derivatives of vegetable oil, for example rapeseed oil, e.g. those obtained by saponification and re-esterification with a monohydric alcohol, can be used as a substitute for diesel fuel. It has recently been reported that mixtures of biofuels, for example, between 5:95 and 10:90 in volume are likely to be available comersially in the future sersano. Thus, a biofuel is a vegetable or animal oil or both or a derivative thereof. Vegetable oils are mainly triglycerides of monocarboxylic acids, e.g. acids containing from 10 to 25 carbon atoms and with the following formula: CH2OCO C I H2OCO I CH2OCO wherein R is an aliphatic radisal of 10 to 25 carbon atoms which may be saturated or unsaturated. Generally, these oils contain glycerides of various acids, varying the number and class are the vegetable source of the oil. Examples of oils are rapeseed oil, coriander oil, soy bean oil, cottonseedseed, sunflowerseed, castor oil, olive oil, peanut oil, corn oil, almondseed, palm, bland soup, mustard sauce, beef tallow and fish oils. Rapeseed oil, which is a mixture of fatty acids particularly esterified with glycerol, is preferred since it is available in large quantities and can be obtained in a simple manner by pressing the rapeseed. Examples of derivatives thereof are alkyl esters, such as methyl esters, or fatty acids from vegetable or animal compounds. These esters can be made by transesterifissation. With respect to the lower alkyl esters of fatty acids, one should have considered the following, as an example of somersial mixtures: ethylic, propyl, butyl and especially methyl esters of fatty acids with 12 to 22 carbon atoms, for example of a hard laurysm, an arid myrrhism, a palmitic acid, an acid palmitoleiso, a harsh stearin, a very fine oleifera, a harsh petroselise, a harsh risinoleiso, a harsh elaeostearose, a harsh linoleic, and a harsh linolense, a harsh eisosanoiso, a harsh gadoleiso, a harsh dososanoiso or a harsh erusic, suals have an iodine number of 50 to 150, especially 90 to 125. The mixtures are particularly advantageous properties are those that are prinsipalmente, is desir to suando minus 50 by weight of methyl esters of fatty acids with 16 to 22 atoms of carbon and 1, 2 or 3 double bonds. Preferred lower alkyl esters of the fatty acids are the methyl esters of oleic acid, linoleic acid, linolenic acid and erusic acid. The somersial meshes of the mentioned slase are obtained, for example, by the segmentation and esterifisation of natural fats and oils by their transesterification with lower aliphatic alcohols. For the production of lower alkyl esters of fatty acids it is advantageous to start from fats and oils with a high number of iodine, such as, for example, sunflower oil, rapeseed oil, silantro sausage, risino sausage, soybeans, cottonseed oil, peanut oil or beef tallow. Lower alkyl esters of the fatty acids based on a new variety of rapeseed oil, the fatty acid component from which more than 80 weight percent of unsaturated fatty acids with 18 carbon atoms are derived, are preferred.

The biosombustibles dessritos previously can be used in mezslas are aseites asexil of petroleum of average distillation. These mixtures typically contain 0 to 10 percent by weight of the biofuel and 90 to 100 percent by weight of the petroleum gasoline., although other relative proportions can also be used for advantageous effect. Particularly useful are mixtures of biofuels with "diesel automotive" type fuel oils which exhibit extremely low levels of sulfur and are therefore particularly prone to lubrication problems. In the fuel oil composition of the first aspect, the consension of the insorporated composition in the composition may be, for example, in the range of 0.5 to 1000 ppm of additive (active ingredient) by weight per weight of the fuel, for example from 1 to 500 ppm such as from 10 to 200 ppm by weight per weight of the fuel, preferably from 20 to 200 ppm, more preferably 25 to 100 ppm. In addition to the medium distillation fuel oils, other fuels that have a need for increased lubrication, such as fuels (eg, future gasoline) intended for high pressure fuel injection equipment, can be conveniently treated with the additives of the invention.

The Fuel Oil Composition of the Second Aspect of the Invention C. The Additive Composition The additive composition defined under the second aspect is prepared by the incorporation of the somo somo is defined under the first aspesto in a somposision that by itself comprises one or more additives for fuel oils. This incorporation can be achieved by stirring or mixing, either an existing composition or with the components thereof, to produce the additive. However, the term "incorporation" within the meaning of this thickened atom extends not only to the physical mixture of the material are other materials, but also to any physical and / or chemical interaction that may result after the introduction of the atom, or after the rest. Many fuel oil additives are known in the art and can be used to form the additive sompostion in which the compound is incorporated. These additives include, for example, the following: detergents, antioxidants, sorrosion inhibitors, de-agurisers, demulsifiers, metal deactivators, antifoaming agents, cetane improvers, combustion improvers, dyes, packaging compatibilizers, other lubricating additives and anti-aesthetic additives. Additives that improve cold flow may also be present.

D. The Composition of Additive Concentrate The consentrate can be obtained by insorporating the composition defined under the first aspect, or the composition of the additive, in a solvent mutually acceptable for them. The resulting mixture can be either a solder or a dispersion, but preferably it is a solution. Suitable solvents include organic solvents including hydrocarbon solvents, for example petroleum fractions such as naphtha, kerosene, diesel and heating oil; aromatic hydrocarbons such as aromatic fractions, e.g. those sold under the somersial marsa "SOLVESSO"; and paraffinic hydrocarbons such as hexane and pentane and also isoparaffins. Other solvents include oligomers and hydrogenated oligomers of alkenes such as decene or hydrogenated decene-1 trimer. Also useful are alcohols and esters, especially higher alcohols such as liquid alkanols having at least 8 sarbone atoms. A particularly useful solvent is isodecanol. Mixtures of these solvents can be used in order to produce a mutually compatible solvent system. The concentrate may contain up to 80 percent by weight, for example 50 percent, of solvent. The consentrate is particularly suitable as a means for incorporating the additive composition in the fuel oil where, despite the presence of the compound, the joint presence of other desired additives in the composition requires a sanctity of solvent in order to impart manageability. However, the consentrados that somprenden the sompuesto as the only additive can also be used, espesialmente suando small amounts of the compound and the equipment present are required for the introduction of the additive sarese of the presision necessary to measure or handle these small volumes. When the composition of asexible asex is produced by the incorporation of the additive composition or consentrate, the sanctity used of any of these compositions will be such as to insure the insorporation to the fuel oil of the required amount of the compound. For example, however, when the composition of additives or concentrate is used, the amount will usually be in the range of 1 to 5000 ppm of the composition (active ingredient) by weight per weight of the fuel, especially from 10 to 2000 ppm such as from 50 to 500 ppm. As indicated above, the composition defined under the first aspect, and the composition of additive and concentrate defined under the second aspect, find the application in non-combustible asexes are under sulfur containment. Another aspect of this invention is therefore the use of the compoundor of the additive composition or concentrate, in an average liquid hydrocarbon distillation fuel oil, having a sulfur concentration of 0.2 weight percent or less, by weight of the fuel, particularly to improve the lubrication thereof. This invention also provides a method for improving the lubrication of a liquid hydrocarbon middle distillate fuel oil having a sulfur consension of 0.2 weight percent based on the weight of the fuel, comprising the addition thereto of the composition or additive concentrate, or compound. The Compound of the Third Aspect The compound claimed under the third aspect comprises one or more hydroxyl derivatives of the formula -OR 'wherein R' is somo is defined in relasion with the first aspect but is not hydrogen. These materials can show good performance as lubrication enhancers and as detergents and / or dispersants in medium distillation fuels with low sulfur content. The invention will now be further described with reference to the examples only as follows: Example 1; Preparation of the Compounds, and the Combustible Oil Composition The compounds as defined under the first aspect of the invention were prepared via the amidifisation of salicylic hydrocarbyl acid substituted with several amines. In each case, the hydrocarbyl substituents in the salicylic acid were normal alkyl groups varying in number of carbon atoms from 14 to 18 and predominantly alkyl with 18 sarbon atoms. The majority of the reastivo of the salísíliso acid was monoalquilado although a proporsión was dialquilada are two of these alkyl groups. The amines used in each preparation are shown in Table 1. The amidation reactions were carried out as follows: Alkylsalicylic acid reaction of 14 to 18 carbon atoms with tetraethylene pentamine fTEPA) To a 5 neck flask were added 100 grams of alkylsalicylic acid (65 per cent of astive ingredient in xylene) and 100 grams of toluene. While stirring under nitrogen, the mixture was heated to 80 ° C. and 16.6 grams of tetraethylenepentamine were added slowly in the dropping funnel (over a period of 15 minutes) to the reassuring flask. The mixture was heated to a reflux temperature of toluene (110aC) for 3 hours. The reassess mixture was filtered by boiling off most of the toluene and heated at 150 ° C. under nitrogen for one hour to decompose the salt in the amide and water. The final product had a TAN of 1.4 and a nitrogen content of 5.54 per cent (weight). Reassesses are N, N-dimethyl-1,3-propanediamine. The above mentioned procedure was repeated with 26.9 grams of the amine. The final product had a TAN of 2.7 and a nitrogen content of 1.67 percent (weight). Reaction with ethane-1.2-diamine. The above reation is repeated is 52.8 grams of the amine. The final produsto had a TAN of 0.6 and a nitrogen snooze of 2.16 per cent (weight). A softened amide was prepared via an intermediate ester, as described below: Preparation of the amide derivative by means of inolysis of the methylisal ester of the alkylsalicylic acid of 14 to 18 carbon atoms (i) Preparation of the methylisal ester of the alkylsalicylic acid in a flask of 5-round round bottom equipped with a mesániso agitator, a nitrogen cooler and a Dean-Stark condenser were placed 329 grams of alkylarylsalicylic acid (65 percent active ingredient in xylene), 349 grams of methanol and 16.7 grams of sulfuric acid 90 percent. The mixture was refluxed at 65-662C for 16.5 hours. The mixture was consented by boiling 322 milliliters of methanol leading to a phase separation of the mixture. The reaction mixture was decanted in a separating funnel and the lower sapa, approximately 40 milliliters which was composed of xylene and sulfuric acid, was removed. The top layer was washed 5 times with 100 milliliters of distilled water and finally dried on a rotary evaporator at 118 aC to give 203 grams of material with a TAN of 81.3 milligrams KOH / g. (ii) Aminolysis of the ester In a 5 neck round bottom flask equipped with a mechanical stirrer, a nitrogen cooler and a Dean Stark condenser was placed 77.5 grams of the ester product prepared above, and 296.2 grams of Solvent 30. The mixture was heated to 70SC and 43.7 grams of N, N-dimethyl-1,3-propanediamine was added over a period of 10 minutes. The mixture was brought to reflux temperature (1089C) and held there for 13 hours. A part of the solvent and the unreacted amine were evaporated. The mixture was finally rotary evaporated under vacuum at 130 ° C to produce 90.3 grams of a product are a TAN of 74.9 and a nitrogen content of 4.8 per cent (weight). In all cases the preparations comprised the desired amide product and a proportion of alkylphenol of 14 to 18 carbon atoms (unreacted from the formation of the salidic acid). The sompositions that were amide of Table 1 were added to 2 low distillation medium distillation saplings are low sulfur containing sarasteristisas shown below.

Fuel A Fuel B Content of 0.02109 0.00045 sulfur (weight per feel) Density (15 ° C, 0.8256 815.3 kg./M3) D 86 Distillation (• C) PEI 157 Not reported 95% 328 279 In the sanctities shown in Table 2, to provide fuel oil compositions according to the invention. The fuel-oil compositions of Example 1 were tested in a high-frequency reciprocating test of Rig (or "RAFR") to determine the lubrication performance and compare it with untreated fuel oil (Comparative No. 1). The high frequency reciprocating test method of Rig is described in the industry standard test methods CEC PF 06-T-94 and ISO / TC22 / SC7 / WG6 / W188 and was carried out at 60 ° C.

The results of the high frequency reciprocating test of Rig are shown in Table 2. In this case it can be seen that the fuel oil sompositions comprising the compound defined under the first aspect of the invention provide improved lubrication performance.

TABLE 1 TABLE 2

Claims (15)

1. NOVELTY OF THE INVENTION Having discussed the above invention, it is considered a novelty and, therefore, is resounding as such property in the following CLAIMS 1. The use of a compound comprising one or more aromatic ring systems where at least one of the ring systems bears, as substituents: (i) one or more hydrocarbyl groups that impart oil solubility to the compound, and (ii) one or more hydroxyl groups, and (iii) one or more amide groups, or of a composition or sonsentrado of additive in which the compound has been incorporated, as an additive in a medium distillate liquid hydrocarbon fuel oil having a sulfur concentration of 0.2 weight percent or less, based on the weight of the fuel , to improve the lubrication of the same.
2. 2. The use according to claim 1 in claim 1 characterized in that the compound has the general formula (I): where Ar represents an aromatic ring system; B represents a hydrocarbyl group (i); OR 'represents a hydroxyl group (ii), CONR "R" *' represents an amide group (iii) wherein R "and R1" each independently represents hydrogen or a hydrocarbyl group or a poly (alkylene-oxy) alkyl group or poly (alkyleneamino) alkyl, optionally substituted by one or more heteroatom-containing groups, and A represents a group of the formula (II): wherein Ar, B, R, R "and R * • 'are previously defined, and A' and A" each independently represent hydrocarbylene groups, and wherein: v represents an integer in the range of 0 to 10; w represents an integer in the range from 0 to 3; and x, y and z each independently represents an integer in the range of 1 to 3.
3. 3. Use in accordance with claim 1 or claim 2 sarasterized because the package comprises an aromatic ring system carrying one of each of the substituents (ii) and (iii).
4. 4. The use according to claim 1 in claim 1 or claim 2 characterized in that the package comprises two or more aromatic ring systems, each ring system carrying one of each of the substituents (ii) and (iii).
5. 5. The use in accordance with that claimed in any of the preceding claims sarasterized because the one or more of the aromatic ring systems of the compound is a single 6-membered ring.
6. 6. The use of conformance is what is recited in claim 5 suando is dependent on claim 3, characterized in that the compound comprises a single benzene ring bearing (i) one or two aliphatic hydrocarbyl substituents, at least one of which contains less than 8 sarbono atoms, and (ii) a hydroxyl group, and (iii) an amide group.
7. 7. The use of claim according to claim any of the above claims sarasterized because the amide group is derivable from an alkylene diamine or polyamine polyalkylene.
8. 8. The use of sonicity is what is recited in claim 7, wherein the compound is the amide formed by the reaction of ethane-1, 2-diamine or tetraethylenepentamine is a very salicylic substituted alkyl, the substituent or the alkyl substituents of the acid They have an average of 14 to 18 atoms of sarbon.
9. 9. A sompossible asepsis composition obtainable by the addition of a minor proportion of a compound comprising one or more aromatic ring systems, wherein at least one of the ring systems bears, as substituents: (i) one or more groups aliphatic hydrocarbyl having from 14 to 36 sarbone atoms, and (ii) one or more hydroxyl groups, and (iii) one or more amide groups derivable from an alkylenediamine or polyalkylene polyamine, at a higher propulsion of a medium distillate fuel oil. liquid hydrocarbon having a sulfur concentration of 0.2 percent by weight or less, based on the weight of the fuel.
10. 10. A combustible oil composition obtainable by addition, to the fuel oil defined in claim 9, of a composition or concentrate of additive in which the composition defined in claim 9 has been insorporated.
11. 11. A method for improving the lubrication of a liquid distillation medium hydrosarburet seizure liquid that it has a sulfur concentration of 0.2 weight percent or less based on the weight of the fuel, which includes the addition thereto of the composition defined in claim 9 of the additive composition or concentrate defined in claim 10.
12. 12. A compound which comprises one or more aromatic ring systems, wherein at least one of the ring systems carries, as substituents; (i) one or more hydrocarbyl groups that impart oil solubility to the compound, and (ii) one or more hydroxyl derivatives with the formula -OR 'wherein R' is hydrosarbyl or a group of the formula Hydrosarbyl (-M-alkylene) --- where M represents an oxygen atom or an NH group and n represents a number from 1 to 50, and (iii) one or more amide groups
13. 13. A somposission of additive in the sual has insorporated the somatic state of the claim 12.
14. 14. An additive concentrate composition obtainable by the incorporation of the somposision of claim 13, or the compound of claim 12, and optionally one or more additional additives, into a mutually compatible solvent therefor. fuel oil composition obtainable by the addition of a minor proportion of the compound defined in claim 12 to a major proportion of an average liquid hydrocarbon distillation fuel having a concentration of Sulfur of 0.2 by weight or less, based on the weight of the fuel.